CN105278241A - Photosensitive thermosetting resin composition, dry film and printed wiring board - Google Patents
Photosensitive thermosetting resin composition, dry film and printed wiring board Download PDFInfo
- Publication number
- CN105278241A CN105278241A CN201510388812.2A CN201510388812A CN105278241A CN 105278241 A CN105278241 A CN 105278241A CN 201510388812 A CN201510388812 A CN 201510388812A CN 105278241 A CN105278241 A CN 105278241A
- Authority
- CN
- China
- Prior art keywords
- heat curing
- curing resin
- resin combination
- photosensitive heat
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The invention relates to a photosensitive thermosetting resin composition, a dry film and a printed wiring board. The invention provides the photosensitive thermosetting resin composition which has excellent flexibiliity and is suitable for an insulating film of a flexible printed circuit board, and particularly suitable for a process in which a bent part (flexible part) and a mounting part (non-flexible part). Furthermore, the invention provides the printed circuit board with the cured object of the composition as a protective film, such as a covering layer or a solder mask. The photosensitive thermosetting resin composition comprises the components of (A) a polyamide-imide resin which is obtained through reaction of a reaction raw material which comprises an imide compound and a diisocyanate compound, wherein the imide compound is obtained through reaction between at least one diamine which comprises ethylenediamine and an anhydride (a1) which comprises tricarboxylic anhydride; (B) a photobase generator; and (C) thermosetting components.
Description
Technical field
The present invention relates to the photosensitive heat curing resin combination of the dielectric film that can be used as flexible printed circuit board, dry film and printed circuit board (PCB).
Background technology
In recent years, along with smart mobile phone, tablet terminal universal, electronic equipment is small-sized slimming gradually, therefore needs the little spatialization of circuit substrate.Therefore, it is possible to the flexible printing of bending storage can expand the purposes of circuit board, flexible printed circuit board also needs to have the reliability up to above up to now.
On the other hand, at present, as the dielectric film of the insulating reliability for guaranteeing flexible printed circuit board, hybrid technique below extensive employing: for bend (deflection division), use using the polyimide of the mechanical property such as thermotolerance and flexibility excellence as matrix overlayer (such as, with reference to patent documentation 1,2), for installation portion (non-deflected portion), use electrical insulating property, resistance to soldering heat performance etc. excellent and the photosensitive polymer combination of retrofit can be carried out.
That is, polyimide is needed as the overlayer of matrix the processing that utilizes mould die-cut, be therefore unsuitable for fine wiring.Therefore, for the chip installation portion needing fine wiring, incorporating aspects is needed to use the alkali development-type photosensitive resin composition (solder resist) that photoetching process can be utilized to carry out processing.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 62-263692 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 63-110224 publication
Summary of the invention
the problem that invention will solve
So, in the manufacturing process of current flexible printed circuit board, there are the following problems: have to adopt the tectal operation of laminating and the hybrid technique of operation forming solder mask, cost-effectivenes and operability poor.
On the other hand, at present, have studied the dielectric film as solder mask or be used as the solder mask of flexible printed circuit board and overlayer as tectal dielectric film, but the material that fully can meet both requirement performances is not yet practical.Particularly, in flexible printed circuit board, be most important for bending permanance, therefore need the solder mask that realizes being used as flexible printed circuit board and overlayer and for the starting material of bending excellent in te pins of durability.
Therefore, the object of the invention is to, there is provided flexibility excellent, be suitable for the dielectric film of flexible printed circuit board, be particularly suitable for the photosensitive heat curing resin combination of the technique simultaneously forming bend (deflection division) and installation portion (non-deflected portion); In addition, provide the solidfied material with said composition as diaphragm, the printed circuit board (PCB) of such as overlayer or solder mask.
for the scheme of dealing with problems
The present inventor etc., in order to solve above-mentioned problem, conduct in-depth research, and found that: by comprising the resin combination of specific polyamide-imide resin, Photobase generator and heat curable component, can solve above-mentioned problem, thus completing the present invention.
Namely, the feature of photosensitive heat curing resin combination of the present invention is, it comprises: (A) polyamide-imide resin, it makes the reaction raw materials reaction containing acid imide compound and diisocyanate cpd and obtains, and this acid imide compound is that at least one diamines making to comprise containing carboxyl diamines reacts with the acid anhydrides (a1) comprising tricarboxylic acid anhydride and obtains; (B) Photobase generator; And (C) heat curable component.
In the present invention, aforementioned acid anhydrides (a1) preferably comprises any one or both in trimellitic anhydride and cyclohexane-1,2,4-tricarboxylic acids-1,2-acid anhydride.In addition, previous reaction raw material preferably also comprises tricarboxylic acid anhydride (a2).And then aforementioned acid anhydrides (a2) preferably comprises any one or both in trimellitic anhydride and cyclohexane-1,2,4-tricarboxylic acids-1,2-acid anhydride.In addition, aforementioned (A) polyamide-imide resin preferably also has aliphatic structure and ehter bond.Now, the aliphatic structure of aforementioned (A) polyamide-imide resin is preferably hexane or cyclohexane.In addition, now, the ehter bond of aforementioned (A) polyamide-imide resin is preferably derived from the polyether structure of the diamines with ehter bond, and this molecular weight with the diamines of ehter bond is preferably more than 200.
And then photosensitive heat curing resin combination of the present invention preferably also comprises (D) polyimide resin, and it has imide ring and phenolic hydroxyl group, now, aforementioned (D) polyimide resin more preferably also has carboxyl.In addition, in the present invention, aforementioned (C) heat curable component is preferably cyclic ether compound.Photosensitive heat curing resin combination of the present invention can be preferred for flexible printed circuit board.
In addition, the feature of dry film of the present invention is, it has the resin bed formed by the photosensitive heat curing resin combination of the invention described above.And then the feature of printed circuit board (PCB) of the present invention is, it possesses and uses the photosensitive heat curing resin combination of the invention described above or the dry film of the invention described above and the solidfied material that formed.
the effect of invention
According to the present invention, flexibility excellence can be realized, be suitable for the dielectric film of flexible printed circuit board, particularly be suitable for the photosensitive heat curing resin combination of the technique simultaneously forming bend (deflection division) and installation portion (non-deflected portion); And there is the printed circuit board (PCB) of its solidfied material as diaphragm.
Accompanying drawing explanation
Fig. 1 is the process chart of an example of the manufacture method schematically showing flexible printed circuit board of the present invention.Wherein, (a) of Fig. 1 is lamination process, (b) of Fig. 1 be light irradiation process, (c) of Fig. 1 is heating process, (d) of Fig. 1 is developing procedure, (e) of Fig. 1 is the 2nd smooth irradiation process, (f) of Fig. 1 is heat curing processes.
description of reference numerals
1 flexible printed circuit board
2 copper circuits
3 resin beds
4 resin beds
5 masks
Embodiment
Below, embodiments of the present invention are described in detail.
The feature of photosensitive heat curing resin combination of the present invention is, it comprises: (A) polyamide-imide resin, it makes the reaction raw materials reaction containing acid imide compound and diisocyanate cpd and obtains, and this acid imide compound is that at least one diamines making to comprise containing carboxyl diamines reacts with the acid anhydrides (a1) comprising tricarboxylic acid anhydride and obtains; (B) Photobase generator; And (C) heat curable component.
In photosensitive heat curing resin combination of the present invention, penetrated by illumination and Photobase generator is activated, using produced alkali as catalyzer, polyamide-imide resin and the heat curable component generation addition reaction with carboxyl is made by heating, aqueous slkali can be utilized thus only to be removed by unexposed portion, like this, retrofit can be carried out by alkali development, can expect to obtain solidfied material excellent in reliability on the other hand.The flexibility of photosensitive heat curing resin combination of the present invention is excellent, and has good developability and resolution, therefore, is suitable for the resin insulating barrier of flexible printed circuit board, such as overlayer, solder mask.
Below, each composition forming photosensitive heat curing resin combination of the present invention is described in detail.
[(A) polyamide-imide resin]
(A) polyamide-imide resin used in the present invention is, make to be obtained by reacting acid imide compound containing at least one diamines containing carboxyl diamines with containing the acid anhydrides (a1) of tricarboxylic acid anhydride, then make the reaction raw materials containing the acid imide compound obtained and diisocyanate cpd react further and the resin that obtains.For above-mentioned reaction raw materials, as described later, on the basis of above-mentioned acid imide compound and diisocyanate cpd, preferably containing going back tricarboxylic acid anhydride (a2).
(diamines)
As containing carboxyl diamines, such as, can enumerate: the diaminobenzoic acid classes such as 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acids, 3,4-diaminobenzoic acids; The amido-phenoxybenzoic acid classes such as two (3-amino-benzene oxygen) benzoic acid of 3,5-, 3,5-two (4-amino-benzene oxygen) benzoic acid; 3,3 '-di-2-ethylhexylphosphine oxide (6-aminobenzoic acid), 3,3 '-diamido-4,4 '-dicarboxylate biphenyl, 4,4 '-diamido-3,3 '-dicarboxylate biphenyl, 4,4 '-diamido-2,2 '-dicarboxylate biphenyl, 4,4 '-diamido-2,2 ', 5, the carboxyl biphenyl compounds such as 5 '-tetracarboxylic biphenyl; 3,3 '-diamido-4,4 '-dicarboxyl diphenyl methane, 3,3 '-dicarboxyl-4,4 '-diaminodiphenyl-methane, 2, two [3-amino-4-carboxyl phenyl] propane of 2-, 2,2-two [4-amino-3-carboxyl phenyl] propane, 2,2-two [3-amino-4-carboxyl phenyl] HFC-236fa, 4,4 '-diamido-2,2 ', 5, the carboxyl diphenyl alkane classes such as carboxyl diphenyl methane such as 5 '-tetracarboxylic diphenyl methane; 3,3 '-diamido-4,4 '-dicarboxydiphenyl ether, 4,4 '-diamido-3,3 '-dicarboxydiphenyl ether, 4,4 '-diamido-2,2 '-dicarboxydiphenyl ether, 4,4 '-diamido-2,2 ', 5, the carboxyl diphenyl ether compounds such as 5 '-tetracarboxylic diphenyl ether; 3,3 '-diamido-4,4 '-dicarboxyl diphenyl sulfone, 4,4 '-diamido-3,3 '-dicarboxyl diphenyl sulfone, 4,4 '-diamido-2,2 '-dicarboxyl diphenyl sulfone, 4,4 '-diamido-2,2 ', 5, the diphenyl sulfone compounds such as 5 '-tetracarboxylic diphenyl sulfone; Two [(carboxyl phenyl) phenyl] alkane compound classes such as two [4-(4-amino-3-carboxyphenoxy) phenyl] propane of 2,2-; They can be used alone or combinationally use aptly by two [(carboxyphenoxy) phenyl] sulphones etc. such as two [4-(4-amino-3-carboxyphenoxy) phenyl] sulfones of 2,2-.
In the present invention, as diamines, need to use containing carboxyl diamines, but also can combinationally use the diamines without carboxyl.As other diamines that can combinationally use, can be used alone or suitably combinationally use general aliphatic diamine, aromatic diamine etc.Specifically, as other diamines, such as, can enumerate: the diamines of 1 benzene nucleus such as p-phenylenediamine (PPD) (PPD), 1,3-diaminobenzene, 2,4-toluene diamines, 2,5-toluene diamines, 2,6-toluene diamines, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 3, the diaminodiphenyl ether classes such as 4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl-methane, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane, 3,3 ', 5,5 '-tetramethyl-4,4 '-diaminodiphenyl-methane, two (4-aminophenyl) thioether, 4,4 '-diaminobenzene anilid, 3,3 '-dichloro-benzidine, 3,3 '-dimethylbenzidine (o-tolidine), 2,2 '-dimethylbenzidine (4,4 '-diamido-2,2 '-dimethyl diphenyl), 3,3 '-dimethoxy benzidine, 2,2 '-dimethoxy benzidine, 3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, 3,3 '-diamino diphenyl sulfide, 3,4 '-diamino diphenyl sulfide, 4,4 '-diamino diphenyl sulfide, 3,3 '-diamino-diphenyl sulfone, 3,4 '-diamino-diphenyl sulfone, DDS, 3,3 '-diaminobenzophenone, 3,3 '-diamido-4,4 '-dichloro benzophenone, 3,3 '-diamido-4,4 '-dimethoxy-benzophenone, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, two (3-aminophenyl) propane of 2,2-, two (4-aminophenyl) propane of 2,2-, 2,2-two (3-aminophenyl)-1,1,1,3,3,3-HFC-236fa, 2,2-two (4-aminophenyl)-1,1,1,3,3,3-HFC-236fa, 3,3 '-diaminodiphenyl sulfoxide, 3,4 '-diaminodiphenyl sulfoxide, 4,4 '-diaminodiphenyl sulfoxide, 3, the diamines of 2 benzene nucleus such as 3 '-dicarboxyl-4,4 '-diaminodiphenyl-methane, two (3-aminophenyl) benzene of 1,3-, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-aminophenyl) benzene, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (3-the amino-benzene oxygen)-4-trifluoromethylbenzene of 1,3-, 3,3 '-diamido-4-(4-phenyl) phenoxy benzophenone, 3,3 '-diamido-4,4 '-two (4-phenylphenoxy) benzophenone, two (3-aminophenyl-thioether) benzene of 1,3-, two (4-aminophenyl-thioether) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl-thioether) benzene, two (the 3-aminophenyl sulfone) benzene of 1,3-, two (the 4-aminophenyl sulfone) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl sulfone) benzene, two (2-(4-aminophenyl) isopropyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(2-(3-aminophenyl) isopropyl) benzene, the diamines of 3 benzene nucleus such as Isosorbide-5-Nitrae-bis-(2-(4-aminophenyl) isopropyl) benzene, 3,3 '-bis-(3-amino-benzene oxygen) biphenyl, 3,3 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, two [3-(3-amino-benzene oxygen) phenyl] ether, two [3-(4-amino-benzene oxygen) phenyl] ether, two [4-(3-amino-benzene oxygen) phenyl] ether, two [4-(4-amino-benzene oxygen) phenyl] ether, two [3-(3-amino-benzene oxygen) phenyl] ketone, two [3-(4-amino-benzene oxygen) phenyl] ketone, two [4-(3-amino-benzene oxygen) phenyl] ketone, two [4-(4-amino-benzene oxygen) phenyl] ketone, two [3-(3-amino-benzene oxygen) phenyl] thioether, two [3-(4-amino-benzene oxygen) phenyl] thioether, two [4-(3-amino-benzene oxygen) phenyl] thioether, two [4-(4-amino-benzene oxygen) phenyl] thioether, two [3-(3-amino-benzene oxygen) phenyl] sulfone, two [3-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [3-(3-amino-benzene oxygen) phenyl] methane, two [3-(4-amino-benzene oxygen) phenyl] methane, two [4-(3-amino-benzene oxygen) phenyl] methane, two [4-(4-amino-benzene oxygen) phenyl] methane, two [3-(3-amino-benzene oxygen) phenyl] propane of 2,2-, two [3-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [3-(3-amino-benzene oxygen) phenyl]-1,1,1,3,3, the 3-HFC-236fa of 2,2-, two [3-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3, the 3-HFC-236fa of 2,2-, two [4-(3-amino-benzene oxygen) phenyl]-1,1,1,3,3, the 3-HFC-236fa of 2,2-, the aromatic diamines such as the diamines of 4 benzene nucleus such as two [4-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3, the 3-HFC-236fa of 2,2-, EDA, 1,3-diaminopropanes, 1,4-diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1,11-diamino undecane, 1, the aliphatic diamines such as 12-diamino dodecane, 1,2-diamino-cyclohexane.
In addition, as the diamines with ehter bond, can enumerate: as the polyethyleneoxide diamine, polypropyleneoxide diamine, polybutylene diamines etc. of polyoxy alkylene diamine.As commercially available product, can enumerate: JEFFAMINEEDR-148, EDR-176, JEFFAMINED-230, D-400, D-2000, D-4000, JEFFAMINEED-600, ED-900, ED-2003, JEFFAMINEXTJ-542 etc. that U.S. HuntsmanCorporation manufactures.The molecular weight with the diamines of ehter bond is preferably more than 200, is more preferably 200 ~ 3000, more preferably 400 ~ 2000.
In addition, as amino-modified silicone, can enumerate: BY16-205, FZ-3760, BY16-871, BY16-853U etc. that DowCorningTorayCo., Ltd. manufacture.
(acid anhydrides (a1) and acid anhydrides (a2))
For acid anhydrides (a1) and acid anhydrides (a2), as tricarboxylic acid anhydride, can enumerate respectively: have in aromatic ring and aliphatics ring at least any one; As the acid anhydrides with aromatic ring, trimellitic anhydride (benzene-1,2,4-tricarboxylic acids 1,2-acid anhydride, TMA) etc. preferably can be enumerated; As the acid anhydrides with aliphatics ring, hydrogenated trimellitic anhydride (cyclohexane-1,2,4-tricarboxylic acids-1,2-acid anhydride, H-TMA) etc. preferably can be enumerated.These acid anhydrides can be used alone one, also can combine two or more use.
In the present invention, as acid anhydrides, need to use above-mentioned tricarboxylic acid anhydride, but also can combinationally use carboxylic acid dianhydride.As carboxylic acid dianhydride, can enumerate: pyromellitic acid anhydride, 3,3 ', 4, the tetracarboxylic anhydrides etc. such as 4 '-benzophenone tetracarboxylic dianhydride.In addition, two tip type carboxylic acid anhydride modified organosilicons etc. can be enumerated.
(diisocyanate cpd)
As diisocyanate cpd, can use: diisocyanate, other general diisocyanates such as aromatic diisocyanate and its isomeride, polymer, aliphatic diisocyanate class, ester ring type diisocyanates and its isomeride, but be not limited to these.In addition, these diisocyanate can be used alone or also can combinationally use.
As diisocyanate, specifically, such as can enumerate: 4, 4 '-methyl diphenylene diisocyanate (MDI), toluene diisocyanate, naphthalene diisocyanate, eylylene diisocyanate, biphenylene diisocyanate, diphenylsulphone diisocyanate, the aromatic diisocyanates such as diphenyl ether diisocyanate and its isomeride, polymer, hexamethylene diisocyanate, isophorone diisocyanate (IPDI), two cyclohexyl methane diisocyanates, xylylene diisocyanate, the aliphatic diisocyanate classes such as trimethyl hexamethylene diisocyanate (TMDI), or by the ester ring type diisocyanates of above-mentioned aromatic diisocyanate hydrogenation and isomeride, or other general diisocyanates.
As mentioned above, for obtaining in the reaction raw materials of polyamide-imide resin, except above-mentioned acid imide compound and diisocyanate cpd, can also containing the acid anhydrides (a2) same with the acid anhydrides used when obtaining acid imide compound.For the content of the acid anhydrides (a2) in reaction raw materials now, there is no particular limitation.Good with the harmony of the mechanical property of solidfied material obtained etc. from the view point of the alkali-solubility making polyamide-imide resin, relative to the amount for obtaining the diamines that the acid imide Chemistry and Physics Institute in reaction raw materials uses, the molar ratio of the amount of the acid anhydrides (a2) in reaction raw materials be preferably more than 0.25 and less than 4, be more preferably more than 0.5 and less than 2, be particularly preferably more than 0.6 and less than 1.5.
For the content of the diisocyanate cpd in reaction raw materials, also there is no particular limitation.Good with the harmony of the mechanical property of solidfied material obtained etc. from the view point of the alkali-solubility making polyamide-imide resin, relative to the summation of the amount of the acid anhydrides (a2) contained in the amount for obtaining the diamines that the acid imide Chemistry and Physics Institute in reaction raw materials uses and reaction raw materials as required, the molar ratio of the amount of the diisocyanate cpd in reaction raw materials be preferably more than 0.3 and less than 1.0, be more preferably more than 0.4 and less than 0.95, be particularly preferably more than 0.50 and less than 0.90.
Particularly, by using the diamines and the H-TMA as the trimellitic acid of ester ring type with ehter bond, (A) polyamide-imide resin obtained becomes the resin that alkali-solubility raises, developability improves, therefore preferably.In addition, from identical reason, in the reaction in the 2nd stage, also preferably aliphatic diisocyanate is used.Think: for imide structure, the stacking provisions of mutually filling owing to taking strand, so low to the dissolubility of solvent, aqueous alkali, but by import aliphatic chain, alicyclic structure and cause stacking provisions be destroyed, thus alkali-solubility improve.
In the present invention, above-mentioned (A) polyamide-imide resin preferably has aliphatic structure and ehter bond.As aliphatic structure now, can enumerate: the hexane of straight-chain or the cyclohexane of ring-type.In addition, above-mentioned ehter bond preferred molecular weight is the polyether structure of more than 200.Imide series resin majority has highly basic/solvent developability, but by importing aliphatic structure, ehter bond, particularly polyether structure, above-mentioned (A) polyamide-imide resin can have weak base developability, depth resolution and flexibility.For above-mentioned aliphatic structure, such as, carboxylic acid one acid anhydride with aliphatics ring can be used or by use, there is the isocyanates of aliphatic structure and import; For above-mentioned ehter bond, such as, can the diamines of aforementioned ehter bond be had by use and import.As the diamines with ehter bond, preferred molecular weight is the diamines of more than 200.
In addition, the amido link of above-mentioned (A) polyamide-imide resin can make isocyanates and carboxylic acid reaction and obtain, and also can be obtained by reaction in addition.Above-mentioned (A) polyamide-imide resin can also have the key formed by other addition and condensation.
In the present invention, for the compounding ratio of each composition during acquisition above-mentioned (A) polyamide-imide resin, relative to above-mentioned diamines 1 mole, above-mentioned acid anhydrides is preferably 2.0 ~ 2.4 moles, is more preferably 2.0 ~ 2.2 moles.For making diamines and anhydride reaction, there is no particular limitation, preferably in the scope of 140 DEG C ~ 200 DEG C for temperature of reaction when carrying out imidizate by dehydration closed-loop.For make above-mentioned diamines and above-mentioned anhydride reaction and the temperature of reaction of the imide compound obtained and diisocyanate cpd there is no particular limitation, preferably in the scope of 130 DEG C ~ 200 DEG C.
For above-mentioned (A) polyamide-imide resin, in order to tackle alkali developing procedure, its acid number is preferably more than 50mgKOH/g, is more preferably 50 ~ 200mgKOH/g, more preferably 70 ~ 130mgKOH/g.When acid number is more than 50mgKOH/g, increase relative to the dissolubility of alkali, developability becomes good, and then, uprise with the degree of crosslinking of the postradiation heat curable component of light, therefore can obtain sufficient development contrast.On the other hand, when acid number is below 200mgKOH/g, can suppress the what is called heat atomization in the postradiation PEB of light described later (POSTEXPOSUREBAKE (post exposure bake)) operation, technique enough and to spare (processmargin) becomes large.
In addition, for the molecular weight of (A) polyamide-imide resin, if consider developability and cured coating film characteristic, then matter average molecular weight is preferably less than 10000, is more preferably 1000 ~ 8000, more preferably 2000 ~ 6000.If molecular weight is less than 10000, then the alkali-solubility in unexposed portion increases, and developability improves.On the other hand, if molecular weight is more than 1000, then in exposure portion, sufficient resistance to developability and solidification physical property after exposure/PEB, can be obtained.
[(B) Photobase generator]
(B) Photobase generator to be penetrated by the illumination of ultraviolet, visible ray etc. and molecular structure changes or molecular cleavage, thus generate and can be used as the compound that the catalyzer with the polyimide resin of carboxyl and the addition reaction of heat curable component plays more than one alkaline matters of function.As alkaline matter, such as, can enumerate: secondary amine, tertiary amine.
As Photobase generator, such as, can enumerate: alpha-aminoacetophenone compound; Oxime ester compound; There is the substituent compound etc. such as acyloxy imino group, N-formylation aromatic series amino, N-acylated aromatic race amino, nitrobenzylamino formic acid ester group, alkoxybenzyl carbamate groups.Wherein, preferred oxime ester compound, alpha-aminoacetophenone compound.As alpha-aminoacetophenone compound, particularly preferably there is the material of two or more nitrogen-atoms.
As other Photobase generator, also can use: WPBG-018 (trade name: 9-anthrylmethylN, N '-diethylcarbamate (9-anthrylmethyl-N, N '-diethylamino formic ether)), WPBG-027 (trade name: (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl] piperidine ((E)-1-[3-(2-hydroxy phenyl)-2-acryloyl group] piperidines)), WPBG-082 (trade name: guanidinium2-(3-benzoylphenyl) propionate (2-(3-benzoylphenyl) propionic acid guanidine)), WPBG-140 (trade name: 1-(anthraquinon-2-yl) ethylimidazolecarboxylate (imidazolyl carboxylic acid 1-(anthraquinone-2-base) ethyl ester)) etc.
Alpha-aminoacetophenone compound has benzoin ehter bond in the molecule, is subject to, when illumination is penetrated, cracking in molecule occurs, and generates the alkaline matter (amine) playing solidification catalytic action.As the concrete example of alpha-aminoacetophenone compound, (4-morpholinyl benzoyl)-1-benzyl-1-dimethylaminopropanecompounds (IRGACURE369 can be used, trade name, BASFJAPANLTD. manufacture), 4-(methylthio phenyl formoxyl)-1-methyl isophthalic acid-morpholinyl ethane (IRGACURE907, trade name, BASFJAPANLTD. manufacture), 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone (IRGACURE379, trade name, BASFJAPANLTD. manufacture) etc. commercially available compound or its solution.
As oxime ester compound, as long as be penetrated by illumination and the compound generating alkaline matter can use arbitrarily.For above-mentioned oxime ester compound, as commercially available product, can enumerate: CGI-325, IRGACUREOXE01, IRGACUREOXE02 that BASFJAPANLTD. manufactures; N-1919, NCI-831 etc. that ADEKACORPORATION manufactures.In addition, also that record in Jap.P. No. 4344400 publication, that there are in molecule 2 oxime ester bases compound is preferably used.
In addition, can also enumerate: the carbazole oxime ester compound etc. recorded in Japanese Unexamined Patent Publication 2004-359639 publication, Japanese Unexamined Patent Publication 2005-097141 publication, Japanese Unexamined Patent Publication 2005-220097 publication, Japanese Unexamined Patent Publication 2006-160634 publication, Japanese Unexamined Patent Publication 2008-094770 publication, Japanese Unexamined Patent Application Publication 2008-509967 publication, Japanese Unexamined Patent Application Publication 2009-040762 publication, Japanese Unexamined Patent Publication 2011-80036 publication.
This Photobase generator may be used alone, can also be used in combination of two or more kinds.Relative to heat curable component 100 mass parts, the compounding amount of the Photobase generator in photosensitive heat curing resin combination is preferably 0.1 ~ 40 mass parts, is more preferably 0.1 ~ 30 mass parts.If the compounding amount of Photobase generator is more than 0.1 mass parts, then can obtain the contrast of the resistance to developability of illumination part/non-irradiation unit preferably.In addition, if the compounding amount of Photobase generator is below 40 mass parts, then the characteristic of solidfied material improves.
[(C) heat curable component]
(C) heat curable component has the material that can pass through the functional group of heat and carboxyl or phenolic hydroxyl group generation addition reaction.As heat curable component, preferably there is the cyclic ether compound of ring-type (sulphur) ether, such as, can enumerate: epoxy resin, multifunctional oxetane compound etc.
Above-mentioned epoxy resin is the resin with epoxy radicals, can use arbitrarily known resin, can enumerate: have the polyfunctional epoxy resin etc. in 2 functionality epoxy resin of 2 epoxy radicals, molecule with multiple epoxy radicals in molecule.In addition, also can be 2 functional epoxide compound through hydrogenation.
As above-mentioned epoxy compound, can enumerate: bisphenol A type epoxy resin, brominated epoxy resin, phenolic resin varnish type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, alicyclic epoxy resin, trihydroxy benzene methylmethane type epoxy resin, di-toluene phenol-type epoxy resin or united phenol-type epoxy resin or their potpourri; Bisphenol-s epoxy resin, bisphenol A novolac type epoxy resin, four hydroxy phenyl ethane type epoxy resin, hetero ring type epoxy resin, o-phthalic acid diglycidyl ester resin, four glycidyl group xylenol ethane resin, copolymerization epoxy resin, CTBN modified epoxy etc. containing Naphthol-based Epoxy Resin, the epoxy resin with dicyclopentadiene skeleton, glycidyl methacrylate copolymerization system epoxy resin, N-cyclohexylmaleimide and glycidyl methacrylate.
As other liquid 2 functionality epoxy resin, can enumerate: vinyl cyclohexene diepoxide, (3 ', 4 '-epoxycyclohexyl-methyl)-3,4-epoxycyclohexane carboxylate, (3 ', 4 '-epoxy-6 '-methylcyclohexylmethyl) cycloaliphatic epoxy resin such as-3,4-epoxy-6-methylcyclohexanecarboxylic acid esters.These epoxy resin can be used alone one, also can combinationally use two or more.
It should be noted that, as (C) heat curable component, also can be compounding: the known usual compounds such as maleimide compound, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resin, cyclic carbonate compound, episulfide resin.
As the compounding amount of (C) heat curable component, be preferably 10:1 ~ 1:10 with the equivalent proportion (carboxyl: the heat reactivity groups such as epoxy radicals) of above-mentioned (A) polyamide-imide resin.By being set to the scope of so compounding ratio, developability becomes good, easily can form fine pattern.Above-mentioned equivalent proportion is more preferably 10:2 ~ 2:10.
[(D) polyimide resin]
Photosensitive heat curing resin combination of the present invention preferably also comprises (D) polyimide resin, and it has imide ring and phenolic hydroxyl group.There is the situation of phenolic hydroxyl group compared with non-existent situation, after exposure be heating and curing in reaction (PEB) operation, can extend under identical heating-up temperature until become the time of alkali resistance by addition reaction, the range of choice of heating-up temperature in PEB operation can also be expanded.Therefore, the operability of photosensitive heat curing resin combination and treatability improve.In addition, unexposed portion also can be suppressed to become the generation of alkali resistance, so-called atomization.For this (D) polyimide resin, as raw material, the amine component of phenolic hydroxyl group can be had by using, isocyanate prepolymer composition synthesizes.
For above-mentioned (D) polyimide resin, as imide ring, preferably there is the part-structure shown in following formula (1).In formula (1), more preferably R contains aromatic rings.
Part-structure shown in above-mentioned formula (1) is more preferably following formula (2) or the structure shown in (3).
Above-mentioned (D) polyimide resin, except imide ring and phenolic hydroxyl group, also preferably has carboxyl, and for the position of the carboxyl in this situation, there is no particular limitation.Can carboxyl be there is as above-mentioned imide ring or with the substituting group of the group of its combination, also can synthesize by using the material with carboxyl as aftermentioned amine component, isocyanate prepolymer composition, thus carboxyl is directed into polyimide resin.
For the synthesis of above-mentioned (D) polyimide resin, known customary way can be used, such as, the method that any one or both in carboxylic acid anhydrides composition and amine component and isocyanate prepolymer composition react can be used.Imidizate can carry out also can carrying out with chemical imidization with hot-imide, in addition, also can combinationally use them to manufacture.
As carboxylic acid anhydrides composition, carboxylic acid one acid anhydride, carboxylic acid dianhydride that above-mentioned (A) polyamide-imide resin is enumerated can be used, but be not limited to these acid anhydrides, as long as have and amino, the anhydride group of isocyanates radical reaction and the compound of carboxyl, just can comprise its derivant and use.These carboxylic acid anhydrides compositions may be used alone, can also be used in combination of two or more kinds.
As the amine component with phenolic hydroxyl group, such as, can enumerate: the diaminobenzene phenols such as 2,4-diaminophenol, 3,3 '-diamido-4,4 '-dihydroxybiphenyl, 4,4 '-diamido-3,3 '-dihydroxybiphenyl, 4,4 '-diamido-2,2 '-dihydroxybiphenyl, 4,4 '-diamido-2,2 ', 5, the hydroxybiphenyl compounds classes such as 5 '-tetrahydroxybiphenyl, 3,3 '-diamido-4,4 '-dihydroxydiphenyl methane, 4,4 '-diamido-3,3 '-dihydroxydiphenyl methane, 4,4 '-diamido-2,2 '-dihydroxydiphenyl methane, 2, two [3-amino-4-hydroxylphenyl] propane of 2-, 2,2-two [4-amino-3-hydroxy base] propane, 2,2-two [3-amino-4-hydroxylphenyl] HFC-236fa, 4,4 '-diamido-2,2 ', 5, the hydroxy diphenyl alkanes such as hydroxy diphenyl methane such as 5 '-tetrahydroxy diphenyl methane, 3, 3 '-diamido-4, 4 '-dihydroxy diphenyl ether, 4, 4 '-diamido-3, 3 '-dihydroxy diphenyl ether, 4, 4 '-diamido-2, 2 '-dihydroxy diphenyl ether, 4, 4 '-diamido-2, 2 ', 5, the hydroxy diphenyl ether compounds such as 5 '-tetrahydroxy diphenyl ether, 3, 3 '-diamido-4, 4 '-dihydroxy-diphenyl sulfone, 4, 4 '-diamido-3, 3 '-dihydroxy-diphenyl sulfone, 4, 4 '-diamido-2, 2 '-dihydroxy-diphenyl sulfone, 4, 4 '-diamido-2, 2 ', 5, the diphenyl sulfone compounds such as 5 '-tetrahydroxy diphenyl sulfone, 2, two [(hydroxy phenyl) phenyl] alkane compound classes such as two [4-(the 4-amino-3-hydroxy oxygen base) phenyl] propane of 2-, two (hydroxyphenoxy) biphenol compound class such as 4,4 '-bis-(4-amino-3-hydroxy oxygen base) biphenyl, 2, two [(hydroxyphenoxy) phenyl] sulphones, 4 such as two [4-(the 4-amino-3-hydroxy oxygen base) phenyl] sulfones of 2-, 4 '-diamido-3,3 '-dihydroxydiphenyl methane, 4, the carboxyl diphenyl alkane classes such as 4 '-diamido-2,2 '-dihydroxydiphenyl methane, 4, two (hydroxyphenoxy) biphenol compound class such as 4 '-diamido-2,2 '-dihydroxydiphenyl methane, 4,4 '-bis-(4-amino-3-hydroxy oxygen base) biphenyl, two (hydroxyphenoxy) benzene compound classes etc. such as two (the 3-amino-4-hydroxy phenoxy group) benzene of 1,3-, 1,3-two (4-amino-3-hydroxy oxygen base) benzene.These amine components can be used alone or combinationally use.
As isocyanate prepolymer composition, can be used alone or combinationally use the diisocyanate that above-mentioned (A) polyamide-imide resin is enumerated.
For the molecular weight of (D) polyimide resin, if consider developability, resistance to developability and the cured coating film characteristic after exposure/PEB, then matter average molecular weight is preferably 1000 ~ 100000, is more preferably 2000 ~ 50000.
In photosensitive heat curing resin combination of the present invention, can compounding thermal curing catalyst.Thermal curing catalyst is used for the heat curable properties of raising (C) heat curable component further and uses, such as, can use the amines such as dicyandiamide, aromatic amine, imidazoles, phosphorus compound, acid anhydrides, two ring type amidine compounds etc.Specifically, can use: imidazoles, dicyandiamide, benzyl dimethyl amine, 4-(the dimethylamino)-N such as imidazoles, 1-benzyl-2-phenylimidazole, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, the amines such as N-dimethyl benzyl amine; The phosphorus compounds etc. such as triphenylphosphine.More specifically, as glyoxaline compound, can enumerate: 1B2PZ, 2E4MZ, 2MZ-A, 2MZ-OK, 2PHZ, 2P4MHZ (ShikokuChemicalsCorporation manufacture); As the blocked isocyanate compounds of dimethyl amine, can enumerate: U-CAT3503N ,-3502T (San-AproLtd. manufacture); As two ring type amidine compounds and its salt, can enumerate: DBU, DBN, U-CATSA102, U-CAT5002 (San-AproLtd. manufacture) etc.These can be used alone one, or also can combine two or more use.
The containing ratio of thermal curing catalyst utilizes common compounding ratio, such as, relative to (C) heat curable component 100 mass parts, is preferably 0.1 mass parts ~ 10 mass parts.
In photosensitive heat curing resin combination of the present invention, also can compounding inorganic filler.Inorganic filler, for suppressing the cure shrinkage of the solidfied material of photosensitive heat curing resin combination, improves the characteristic such as adaptation, hardness.As inorganic filler, such as, can enumerate: barium sulphate, barium titanate, amorphous silica, crystallinity silicon dioxide, fused silica, spherical silicon dioxide, talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, silicon nitride, aluminium nitride, boron nitride, Nuo Yibao tripoli etc.These can be used alone one, or combine two or more use.
In photosensitive heat curing resin combination of the present invention, also can compounding colorant.As colorant, the usual known colorants such as red, blue, green, yellow, white, black can be used, pigment, dyestuff, pigment.
In order to improve flexibility, the dry to touch of the solidfied material of acquisition, can compounding known usual macromolecule resin in photosensitive heat curing resin combination of the present invention.As macromolecule resin, can enumerate: cellulose-based, Polyester, phenoxy resin based polymer; Pioloform, polyvinyl acetal system, polyvinyl butyral system, polyamide-based, polyimide system, polyamidoimide system binder polymer; End-capped copolymer; Elastic body etc.Macromolecule resin can be used alone one, also can combinationally use two or more.
In photosensitive heat curing resin combination of the present invention, in order to prepare resin combination, in order to adjust viscosity when coating base material, carrier film, can be with an organic solvent.As this organic solvent, can enumerate: ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, petroleum solvent etc.This organic solvent can be used alone one, also can use with the form of potpourri of more than two kinds.
In photosensitive heat curing resin combination of the present invention, can also add as required: the known usual composition such as photopolymerization monomer, sulfhydryl compound, closely sealed promoter (adaptation imparting agent), antioxidant, ultraviolet light absorber, thickening agent, defoamer, levelling agent, silane coupling agent, rust preventive.As thickening agent wherein, such as, can enumerate: fine particle silica, hydrotalcite, organobentonite, smectite etc., as defoamer, such as, can enumerate: silicon-type, fluorine system, macromolecular etc.It should be noted that, relative to above-mentioned (A) polyamide-imide resin 100 mass parts, the compounding amount of photopolymerization monomer is preferably below 15 mass parts, is more preferably below 10 mass parts, most preferably is 0 mass parts (not comprising).
The flexibility of the solidfied material obtained by photosensitive heat curing resin combination of the present invention and excellent heat resistance, and retrofit can be carried out by alkali development, therefore, according to the present invention, incorporating aspects is not needed to use alkali development-type photosensitive resin composition for polyamide-imide resin, may be used for the bend of flexible printed circuit board and any person of installation portion, be suitable for the technique simultaneously forming bend and installation portion.
Dry film of the present invention has following characteristics: it has the resin bed formed by the photosensitive heat curing resin combination of the invention described above.When carrying out dry film, such as, with an organic solvent dilute photosensitive heat curing resin combination of the present invention to be adjusted to suitable viscosity, and be coated into uniform thickness on a carrier film by known methods such as comma coater.Then, usually by drying at the temperature of 50 ~ 130 DEG C 1 ~ 30 minute, resin bed can be formed on a carrier film.
As carrier film, plastic sheeting can be used.For the thickness of carrier film, there is no particular limitation, but usually suitably select the scope of 10 ~ 150 μm.Formed on a carrier film after resin bed, can also on the surface of resin bed stacked strippable coverlay.
In addition, printed circuit board (PCB) of the present invention has following characteristics: it possesses and uses the photosensitive heat curing resin combination of the invention described above or the dry film of the invention described above and the solidfied material that formed.The flexibility of photosensitive heat curing resin combination of the present invention is excellent, and therefore, printed circuit board (PCB) of the present invention can be particularly useful as flexible printed circuit board.
When using photosensitive heat curing resin combination of the present invention to form the resin insulating barrier of printed circuit board (PCB), preferred manufacture method is as described below.That is, a manufacture method, it comprises: resin bed formation process, forms the resin bed formed by photosensitive heat curing resin combination of the present invention on a printed circuit; Light irradiation process, irradiates light to resin bed with pattern-like; Heating process (PEB), heated resin layer; And developing procedure, alkali development is carried out to resin bed, forms the figuratum resin insulating barrier of tool.In addition, as required, after alkali development, carry out that illumination is penetrated, be heating and curing (Post RDBMS), and resin combination is solidified completely further, thus obtain the high resin insulating barrier of reliability.In photosensitive heat curing resin combination of the present invention, utilize the catalytic action of penetrating the alkali produced by (B) Photobase generator based on illumination, by the carboxyl of (A) polyamide-imide resin and the heat curable component generation addition reaction in exposure portion because of heating, thus alkali can be utilized to develop form the pattern of minus.
[resin bed formation process]
In this operation, at least form the resin bed that one deck is formed by above-mentioned photosensitive heat curing resin combination on a printed circuit.As the method forming resin bed, can enumerate: rubbing method and laminating.When for rubbing method, utilize the methods such as serigraphy to be coated with above-mentioned photosensitive heat curing resin combination on a printed circuit, and form resin bed by dry.When for laminating, first, be adjusted to suitable viscosity with organic solvent diluting above-mentioned photosensitive heat curing resin combination, be applied in carrier film also dry, make the dry film with resin bed.Then, utilize laminating machine etc., after making this dry film fit in printed circuit board (PCB) in the mode that resin bed contacts with printed circuit board (PCB), peel off carrier film.
Wherein, between resin bed and printed circuit board (PCB), can other layer of sandwiched.Other layer this is preferably formed by alkali development-type photosensitive resin composition.As alkali development-type photosensitive resin composition, known composition can be used, such as, the known composition of overlayer use or solder mask can be used.By forming this stepped construction comprising other layer, resistance to impact and the more excellent solidfied material of flexibility can be obtained.
[light irradiation process]
In this operation, penetrating by carrying out illumination with the pattern-like of minus, making Photobase generator activation contained in resin bed, and illumination part is solidified.In this operation, due to the alkali that illumination part produces, Photobase generator destabilization, is chemically bred by alkali, thus fully can be cured to the deep of resin bed.As light irradiating machine, direct drawing apparatus can be used, be equipped with the light irradiating machine etc. of metal halide lamp.The mask that the illumination of pattern-like is penetrated is the mask of minus.
Hit the active energy beam of use as illumination, preferably use maximum wavelength to be in laser or the scattered light of the scope of 350 ~ 450nm.By maximum wavelength is set to this scope, can Photobase generator be effectively made to activate.As long as use the laser of this scope, then gas laser, solid-state laser.In addition, its light exposure is different from thickness etc., but usually can be set to 100 ~ 1500mJ/cm
2.
[heating process]
In this operation, after illumination is penetrated, by heated resin layer, illumination part is solidified.Utilize this operation, by the alkali produced in light irradiation process, can deep be cured to.Heating-up temperature is such as 80 ~ 140 DEG C.Heat time is such as 1 ~ 100 minute.The ring-opening reaction of solidification owing to being such as the epoxy resin caused by thermal response of photosensitive heat curing resin combination of the present invention, therefore, reacts compared with the situation of solidifying and carrying out with utilizing optical free radical, can suppress strain, cure shrinkage.
[developing procedure]
In this operation, remove illumination part by alkali development, form the dielectric film of the pattern-like of minus, particularly form overlayer and solder mask.As developing method, the known method of impregnating can be used.In addition, as developer solution, can use: aqueous alkali or their mixed liquors such as the imidazoles such as sodium carbonate, sal tartari, potassium hydroxide, amine, glyoxal ethyline, tetramethylammonium hydroxide aqueous solution (TMAH).It should be noted that, after developing procedure, illumination can also be carried out to dielectric film and penetrate.In addition, such as, also can heat with more than 150 DEG C.
Then, the process chart based on Fig. 1 illustrates by an example of the method for photosensitive heat curing resin combination manufacturing flexible printed circuit board (PCB) of the present invention.It should be noted that, in Fig. 1, although illustrate that resin bed is the situation of stepped construction, also can be situation about only being formed by 1 layer.
In the lamination process of Fig. 1, the laminate structure formed by resin bed 3 and resin bed 4 is formed at the flexible print circuit base material 1 being formed with copper circuit 2.Resin bed 3 is formed by the photosensitive polymer combination comprised containing the alkali developable of carboxy resin etc.In addition, resin bed 4 is formed by the photosensitive heat curing resin combination of the present invention comprising above-mentioned polyamide-imide resin, Photobase generator and heat curable component.
The light irradiation process of Fig. 1 is on resin bed 4, configure mask 5, penetrates by carrying out illumination with the pattern-like of minus, makes Photobase generator activation contained in photosensitive heat curing resin combination, thus the operation that illumination part is solidified.The heating process of Fig. 1 is, after light irradiation process, by heated resin layer, and the operation (PEB operation) that illumination part is solidified.The developing procedure of Fig. 1 is, by utilizing alkaline aqueous solution to develop, removes non-irradiation unit, thus forms the operation of the patterned layer of minus.
It should be noted that, the 2nd smooth irradiation process of Fig. 1 is, as required, for the operation making alkali produce the activation of the Photobase generator of remnants; Heat curing processes is, as required, for the operation making patterned layer fully carry out heat curing.
Embodiment
Below, utilize embodiment, comparative example illustrates the present invention in further detail, but the present invention is not limited to these embodiments, comparative example.
< synthesis example 1: the synthesis example > of polyamideimide resin solution
At room temperature, to the removable there-necked flask input 3 being provided with stirring machine, nitrogen ingress pipe, fractionating column, cooling tube, 5-diaminobenzoic acid 3.8g, 2, (HuntsmanCorporation manufactures 2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane 6.98g, JEFFAMINEXTJ-542, molecular weight 1025.64) 8.21g, gamma-butyrolacton 86.49g, make it dissolve.
Then, drop into cyclohexane-1,2,4-tricarboxylic acids-1,2-acid anhydride 17.84g and trimellitic anhydride 2.88g, at room temperature keep 30 minutes.Then, add toluene 30g, be warming up to 160 DEG C, distill removing toluene and water stir 3 hours, be then cooled to room temperature, obtain acid imide compound solution.
In the acid imide compound solution obtained, drop into trimellitic anhydride 9.61g and trimethyl hexamethylene diisocyanate 17.45g, stir 32 hours at temperature 160 DEG C.So obtain the polyamideimide resin solution (PA-1) with carboxyl.The solid constituent of the resin solution (PA-1) obtained is 40.1 quality %, and the acid number of solid constituent is 83.1mgKOH.
< synthesis example 2: the synthesis > with the polyimide resin solution of imide ring, phenolic hydroxyl group and carboxyl
To be provided with stirring machine, nitrogen ingress pipe, fractionating column, cooling tube removable there-necked flask add 3,3 '-diamido-4,4 '-dihydroxydiphenylsulisomer 22.4g, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane 8.2g, NMP30g, gamma-butyrolacton 30g, 4,4 '-oxygen two phthalic anhydride 27.9g, trimellitic anhydride 3.8g, under nitrogen atmosphere, room temperature, stir 4 hours with 100rpm.Then, add toluene 20g, distill under silicon bath temperature 180 DEG C, 150rpm removing toluene and water stir 4 hours, obtain the alkali-solubility resin solution with imide ring.
The acid number of the resin (solid constituent) obtained is 18mgKOH, Mw is 10000, hydroxyl equivalent is 390.
The preparation > of < photosensitive heat curing resin combination
According to the material recorded in the formula recorded in following table 1 respectively compounding embodiment and comparative example, carry out premixed with stirring machine, then carry out mixing with triple-roller mill, prepare photosensitive heat curing resin combination.It should be noted that, in table, the value of compounding amount represents the mass parts of solid constituent in case of no particular description.
Prepare the flexible print circuit base material being formed with circuit of thick 18 μm of copper, the MECBRITECB-801Y using MECCo., Ltd. to manufacture, carries out pre-treatment.Then, on the flexible print circuit base material carrying out pre-treatment, the mode becoming 25 μm with dried thickness is coated with each photosensitive heat curing resin combination.Then, utilize heated air circulation type kiln dried 90 DEG C/30 minutes, form the overlay film formed by photosensitive heat curing resin combination.
< alkali-developable (patterning) and flexibility evaluate >
For the base material possessed by the overlay film of above-mentioned acquisition, the HMW680GW (metal halide lamp, scattered light) utilizing ORCCORPORATION to manufacture, by exposure 500mJ/cm
2carry out illumination with the pattern-like of minus to penetrate.Then, carry out heating for 60 minutes at 90 DEG C.Then, 30 DEG C, base material dipping is carried out development in 3 minutes in the aqueous sodium carbonate of 1 quality %, that evaluates alkali-developable could.
Then, use heated air circulation type drying oven to carry out thermal treatment in 150 DEG C/60 minutes, obtain the cured coating film of pattern-like.MIT test (using the base material of UPILEX12.5 μm that R=0.38mm/UBEINDUSTRIES, LTD. manufacture) is implemented to the cured coating film obtained, evaluates flexibility.As long as more than 120 cycles left and right, just can meet the flexibility as flexible printed circuit board.
< resolution >
Copper has with thickness 25 μm of formation the cured product pattern of each photosensitive heat curing resin combination of opening footpath φ 200 μm, utilizes SEM (scanning electron microscope) to observe.Confirm the opening shape obtained, evaluate according to following benchmark.
Zero: opening shape is good
×: opening shape is bad
table 1
Note: the compounding amount in table represents with solid constituent (mass parts).
* 1) polyamide-imide resin 1, PA-1 (resin of synthesis example 1)
* 2) polyamide-imide resin 2 (having imide ring and amido link), SOXR-M, NIPPONKODOSHICORPORATION manufacture, without acid number molecular weight 10700
* 3) alkali-developable resin 1, NegamiChemicalIndustrialCo., Ltd. manufactures, acid number 50mgKOH/g polyurethane
* 4) alkali-developable resin 2, KyoeishaChemicalCo., Ltd. manufactures, acid number 47mgKOH/g urethane acrylate
* 5) alkali-developable resin 3, NipponKayakuCo., Ltd. manufactures, acid number 98mgKOH/g bisphenol-f type acrylate resin
* 6) imide resin (there is phenolic hydroxyl group and carboxyl), PI-1 (resin of synthesis example 2)
* 7) E828, Mitsubishi chemical Co., Ltd manufactures, bisphenol A type epoxy resin, epoxide equivalent 190g/eq
* 8) OXE02, BASFJAPANLTD. manufacture, oxime system Photoepolymerizationinitiater initiater
Evaluation result as shown in Table 1 can confirm: the developability of the photosensitive heat curing resin combination of each embodiment and excellent in resolution, and has good flexibility.On the other hand, in comparative example 1, owing to using the polyamide-imide resin without carboxyl, and not compounding (C) heat curable component, therefore, do not obtain developability and resolution.In addition, the result from comparative example 2 ~ 4: when using the alkali-developable resin except polyamide-imide resin, although developability and resolution are well, flexibility can become insufficient.
Claims (13)
1. a photosensitive heat curing resin combination, is characterized in that, it comprises:
(A) polyamide-imide resin, it makes the reaction raw materials reaction containing acid imide compound and diisocyanate cpd and obtains, and this acid imide compound is that at least one diamines making to comprise containing carboxyl diamines reacts with the acid anhydrides (a1) comprising tricarboxylic acid anhydride and obtains;
(B) Photobase generator; And
(C) heat curable component.
2. photosensitive heat curing resin combination according to claim 1, wherein, described acid anhydrides (a1) comprises any one or both in trimellitic anhydride and cyclohexane-1,2,4-tricarboxylic acids-1,2-acid anhydride.
3. photosensitive heat curing resin combination according to claim 1 and 2, wherein, described reaction raw materials also comprises tricarboxylic acid anhydride (a2).
4. photosensitive heat curing resin combination according to claim 3, wherein, described acid anhydrides (a2) comprises any one or both in trimellitic anhydride and cyclohexane-1,2,4-tricarboxylic acids-1,2-acid anhydride.
5. the photosensitive heat curing resin combination according to any one in Claims 1 to 4, wherein, described (A) polyamide-imide resin also has aliphatic structure and ehter bond.
6. photosensitive heat curing resin combination according to claim 5, wherein, the aliphatic structure of described (A) polyamide-imide resin is hexane or cyclohexane.
7. the photosensitive heat curing resin combination according to claim 5 or 6, wherein, the ehter bond of described (A) polyamide-imide resin is the polyether structure being derived from the diamines with ehter bond, and this molecular weight with the diamines of ehter bond is more than 200.
8. the photosensitive heat curing resin combination according to any one in claim 1 ~ 7, it also comprises (D) has the polyimide resin of imide ring and phenolic hydroxyl group.
9. photosensitive heat curing resin combination according to claim 8, wherein, described (D) polyimide resin also has carboxyl.
10. the photosensitive heat curing resin combination according to any one in claim 1 ~ 9, wherein, described (C) heat curable component is cyclic ether compound.
11. photosensitive heat curing resin combinations according to any one in claim 1 ~ 10, it is for flexible printed circuit board.
12. 1 kinds of dry films, is characterized in that, it has the resin bed formed by the photosensitive heat curing resin combination described in any one in claim 1 ~ 11.
13. 1 kinds of printed circuit board (PCB)s, is characterized in that, it possesses and uses the photosensitive heat curing resin combination described in any one in claim 1 ~ 11 or dry film according to claim 12 and the solidfied material that formed.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-138610 | 2014-07-04 | ||
| JP2014138610 | 2014-07-04 | ||
| JP2015100741A JP6568715B2 (en) | 2014-07-04 | 2015-05-18 | Photosensitive thermosetting resin composition, dry film and printed wiring board |
| JP2015-100741 | 2015-05-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105278241A true CN105278241A (en) | 2016-01-27 |
| CN105278241B CN105278241B (en) | 2020-08-11 |
Family
ID=55147504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510388812.2A Active CN105278241B (en) | 2014-07-04 | 2015-07-03 | Photosensitive thermosetting resin composition, dry film and printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105278241B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705387A (en) * | 2018-12-27 | 2019-05-03 | 广东生益科技股份有限公司 | A kind of halogen-free resin composition, flexible printed-circuit board cover film and flexible printed-circuit board comprising it |
| CN111886293A (en) * | 2018-03-28 | 2020-11-03 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, and electronic component |
| CN113166410A (en) * | 2018-11-30 | 2021-07-23 | 太阳油墨制造株式会社 | Photosensitive thermosetting resin composition, dry film and printed wiring board |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10316753A (en) * | 1997-05-21 | 1998-12-02 | Toyobo Co Ltd | Photosensitive heat-resistant resin and varnish |
| JPH10316754A (en) * | 1997-05-21 | 1998-12-02 | Toyobo Co Ltd | Photosensitive heat-resistant resin and varnish |
| CN1416452A (en) * | 2000-03-06 | 2003-05-07 | 日立化成工业株式会社 | Resin compon, heat-resistant resin paste and semiconductor device using them and method for manufacture thereof |
| CN101597462A (en) * | 2008-06-04 | 2009-12-09 | 日立卷线株式会社 | Polyamide-imide resin insulating coating material and the insulated line that has used this coating |
| CN103257527A (en) * | 2008-08-27 | 2013-08-21 | 日立化成工业株式会社 | Photosensitive adhesive composition, and film adhesive, adhesive sheet, adhesive pattern, semiconductor wafer and semiconductor device |
-
2015
- 2015-07-03 CN CN201510388812.2A patent/CN105278241B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10316753A (en) * | 1997-05-21 | 1998-12-02 | Toyobo Co Ltd | Photosensitive heat-resistant resin and varnish |
| JPH10316754A (en) * | 1997-05-21 | 1998-12-02 | Toyobo Co Ltd | Photosensitive heat-resistant resin and varnish |
| CN1416452A (en) * | 2000-03-06 | 2003-05-07 | 日立化成工业株式会社 | Resin compon, heat-resistant resin paste and semiconductor device using them and method for manufacture thereof |
| CN101597462A (en) * | 2008-06-04 | 2009-12-09 | 日立卷线株式会社 | Polyamide-imide resin insulating coating material and the insulated line that has used this coating |
| CN103257527A (en) * | 2008-08-27 | 2013-08-21 | 日立化成工业株式会社 | Photosensitive adhesive composition, and film adhesive, adhesive sheet, adhesive pattern, semiconductor wafer and semiconductor device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111886293A (en) * | 2018-03-28 | 2020-11-03 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, and electronic component |
| CN113166410A (en) * | 2018-11-30 | 2021-07-23 | 太阳油墨制造株式会社 | Photosensitive thermosetting resin composition, dry film and printed wiring board |
| CN109705387A (en) * | 2018-12-27 | 2019-05-03 | 广东生益科技股份有限公司 | A kind of halogen-free resin composition, flexible printed-circuit board cover film and flexible printed-circuit board comprising it |
| CN109705387B (en) * | 2018-12-27 | 2021-07-06 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover film for flexible printed circuit board containing same and flexible printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105278241B (en) | 2020-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6568715B2 (en) | Photosensitive thermosetting resin composition, dry film and printed wiring board | |
| TWI688475B (en) | Laminated structure, dry film and flexible printed wiring board | |
| TWI614571B (en) | Laminated structure, flexible printed wiring board and method of manufacturing same | |
| CN105378564B (en) | Photosensitive thermosetting resin composition and flexible printed circuit board | |
| CN105683836B (en) | Photosensitive heat curing resin combination and flexible printed circuit board | |
| CN105683837B (en) | Photosensitive thermosetting resin composition and flexible printed circuit board | |
| CN107850847B (en) | Laminated structure, dry film, and flexible printed circuit board | |
| JP6549848B2 (en) | Laminated structure | |
| JP2018172533A (en) | Curable resin composition, laminated structure, cured product thereof, and electronic component | |
| JP5903127B2 (en) | Positive photosensitive thermosetting resin composition, dry film and printed wiring board | |
| CN105278241A (en) | Photosensitive thermosetting resin composition, dry film and printed wiring board | |
| JP6568712B2 (en) | Photosensitive thermosetting resin composition, dry film and printed wiring board | |
| KR102288053B1 (en) | Photosensitive thermosetting resin composition and flexible printed wiring board | |
| CN108693702A (en) | Hardening resin composition, laminate structure, its solidfied material and electronic unit | |
| TWI685281B (en) | Laminated structure | |
| JP6050180B2 (en) | Laminated structure and flexible printed wiring board | |
| JP2019001967A (en) | Curable resin composition, laminate structure, cured product of the same, and electronic component | |
| TWI847801B (en) | Curable resin composition, laminated structure, cured product and electronic component | |
| CN106796395A (en) | Dry film and flexible printed circuit board | |
| JP6050181B2 (en) | Method for manufacturing flexible printed wiring board and flexible printed wiring board | |
| CN116847983A (en) | Laminated structure and flexible printed circuit board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230606 Address after: Saitama Prefecture, Japan Patentee after: TAIYO HOLDINGS Co.,Ltd. Address before: Saitama Prefecture, Japan Patentee before: TAIYO INK MFG. Co.,Ltd. |